Method of fabricating pattern structure

ABSTRACT

A method includes forming mask patterns spaced apart from each other by at least one opening on an etch target layer, filling the opening with a block copolymer material including first and second polymer blocks of different properties, and annealing the block copolymer material to form first patterns and second patterns, the first patterns in contact with facing sidewalls of adjacent ones of the mask patterns, respectively, and at least one of the second patterns between the first patterns. The first patterns include the first polymer blocks and the second patterns include the second polymer blocks.

CROSS-REFERENCE T(I) RELATED APPLICATIONS

This US non-provisional patent application claims priority under 35 USC§119 to Korean Patent Application No. 10-2015-0069584, tiled on May 19,2015, the entirety of which is hereby incorporated by reference.

BACKGROUND

1. Field

Some example embodiments of the present disclosure relate to methods offabricating a pattern structure and/or to methods of fabricating apattern structure with improved reliability and integration density.

2. Description of the Related Art

Due to their smaller size, multifunctionality, and/or relativelylow-cost characteristics, semiconductor devices have been used in theelectronics industry. However, integration density of semiconductordevices continues to increase with the advance in the electronicsindustry, which results in various problems. For example, due toincreased integration density of a semiconductor device, width and/orspaced distance of patterns in the semiconductor device decreases whileheight and/or aspect ratio of the patterns increases. Accordingly,distribution of a deposition process and/or an etch process of thinfilms are deteriorated, thereby decreasing reliability of thesemiconductor device.

SUMMARY

Some example embodiments of the present disclosure relate to methods offabricating a relatively highly integrated pattern structure withimproved reliability.

According to some example embodiments of the inventive concepts, amethod of fabricating a pattern structure includes forming mask patternson an etch target layer, the mask patterns spaced apart from each otherby at least one opening, filling the opening with a block copolymermaterial including first and second polymer blocks of differentproperties, and annealing the block copolymer material to form firstpatterns and second patterns, the first patterns in contact with facingsidewalk of adjacent ones of the mask patterns, respectively, and atleast one of the second patterns between the first patterns, the firstpatterns including the first polymer blocks and the second patternsincluding the second polymer blocks.

In some example embodiments, a width of the opening may be smaller thanor equal to a length of a unit of a block sequence in the blockcopolymer material, the block sequence including the first polymerblock-the second polymer block-the second polymer block-the firstpolymer block.

In some example embodiments, the first polymer block-the second polymerblock-the second polymer block-the first polymer block may be arrangedsequentially from one of the facing sidewalls of the adjacent maskpatterns to another of the facing sidewalls of the adjacent maskpatterns in a horizontal direction.

In some example embodiments, each of the mask patterns may behydrophobic, each of the first patterns may be hydrophobic, and thesecond patterns may be hydrophilic.

In some example embodiments, the block copolymer material may includepolystyrene-block-polymethylmethacrylate (PS-b-PMMA), the first polymerblock may include polystyrene (PS), and the second polymer block mayinclude polymethylmethacrylate (PMMA).

In some example embodiments, the method may further include selectivelyremoving the second patterns, and etching the etch target layer usingthe first patterns and the mask patterns as etch masks to form thepattern structure.

In some example embodiments, the block copolymer material may includepolystyrene-block-polydimethylsiloxane (PS-b-PDMS), the second polymerblock may include polystyrene (PS), and the second polymer block mayinclude polydimethylsiloxane (PDMS).

In some example embodiments, the method may further include forming aneutral layer on the block copolymer material and the mask patternsbefore annealing the block copolymer material.

In some example embodiments, the method may further include removing thefirst patterns and the mask patterns, and etching the etch target layerusing the second patterns as an etch mask to form the pattern structure.

In some example embodiments, each of the mask patterns may extend in onedirection, widths of the mask patterns may be equal to each other, andthe opening may include a first opening having a first width and asecond opening having a second width smaller than the first width.

In some example embodiments, the first width may be equal to a length ofthe unit of a block sequence in the block copolymer material, the blocksequence including the first polymer block-the second polymer block-thesecond polymer block-the first polymer block in the block copolymerblock.

In sonic example embodiments, surfaces of the mask patterns arehydrophilic, and the method may further include hydrophobicallymodifying surfaces the hydrophilic surfaces of the mask patterns.

In some example embodiments, each of the first patterns may behydrophobic, and the second patterns may be hydrophilic.

According to other example embodiments of inventive concepts, a methodof fabricating a pattern structure includes forming a mask layer on anetch target layer, forming a sacrificial pattern on the mask layerextending in a first direction, the sacrificial pattern having a linearstructure of a first width, forming spacers on sidewalls of thesacrificial pattern to define a first opening exposing a top surface ofthe mask layer, the first opening having a second width different fromthe first width, removing the sacrificial pattern to form a secondopening having the first width, etching the mask layer using the spacersas etch masks to form mask patterns, the mask patterns defining a thirdopening having the first width and a fourth opening having the secondwidth, filling each of the third and fourth openings with a blockcopolymer material including first and second polymer blocks ofdifferent properties, and annealing the block copolymer material to formfirst patterns and second patterns, the first patterns in contact withfacing sidewalk of adjacent ones of the mask patterns, respectively, andat least one of the second patterns between the first patterns, thefirst patterns including the first polymer blocks and the secondpatterns including the second polymer blocks.

According to yet other example embodiments, a method includes forming ablock copolymer layer between adjacent mask patterns, the blockcopolymer layer including first polymer blocks and second polymer blocksdifferent from the first polymer blocks, and annealing the blockcopolymer layer in order to form first polymer block patterns and atleast one second polymer block pattern, the first polymer block patternsat respective sidewalls of the adjacent mask patterns and the secondpolymer block pattern between the first polymer block patterns, thefirst polymer block patterns including the first polymer blocks and thesecond polymer block pattern including the second polymer blocks.

In yet other example embodiments, the block copolymer layer may beformed in a trench between the adjacent mask patterns, and the trenchmay have a width that is smaller than or equal to a length of a unit ofa block sequence of the block copolymer layers, the block sequenceincluding the first polymer block-the second polymer block-the secondpolymer block-the first polymer block.

In yet other example embodiments, the first polymer block-the secondpolymer block-the second polymer block-the first polymer block of theblock sequence are arranged sequentially from one of the sidewalls ofthe adjacent mask patterns to another of the sidewalls of the adjacentmask patterns in a horizontal direction.

In yet other example embodiments, the method may further include formingthe mask patterns on an etch target layer, selectively removing thesecond polymer block pattern after the annealing, and etching the etchtarget layer using the first polymer block patterns and the maskpatterns as etch masks to form the pattern structure.

In yet other example embodiments, the method may further include formingthe mask patterns on an etch target layer, removing the first polymerblock patterns and the mask patterns after the annealing, and etchingthe etch target layer using the second polymer block pattern as an etchmask to form the pattern structure.

In yet other example embodiments, the method may further include forminga neutral layer on the block copolymer layer and the mask patternsbefore the annealing.

BRIEF DESCRIPTION OF THE DRAWINGS

Some example embodiments of inventive concepts will become more apparentin view of the attached drawings and accompanying detailed description.The example embodiments depicted therein are provided by way of example,not by way of limitation, wherein like reference numerals refer to thesame or similar elements. The drawings are not necessarily to scale,emphasis instead being placed upon illustrating aspects of some of theexample embodiments of the inventive concepts.

FIG. 1, FIGS. 2A and 2B, and FIG. 3 illustrate a block copolymer.

FIGS. 4 to 8 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

FIGS. 9 to 13 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

FIGS. 14 to 17 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

FIGS. 18 to 22 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

FIGS. 23 and 24 are cross-sectional views illustrating a semiconductordevice according to some example embodiments of inventive concepts.

FIG. 25 is a block diagram illustrating an example of an electronicsystem including a semiconductor device fabricated according to someexample embodiments of inventive concepts.

FIG. 26 is a block diagram of a memory card including a semiconductordevice fabricated according to some example embodiments of inventiveconcepts.

DETAILED DESCRIPTION

The advantages and features of the example embodiments of the inventiveconcepts and methods of achieving them will be apparent from thefollowing example embodiments that will be described in more detail withreference to the accompanying drawings. It should be noted, however,that the inventive concepts are not limited to the following exampleembodiments, and may be implemented in various forms. Accordingly, theexample embodiments are provided only to disclose the inventive conceptsand let those skilled in the art know the category of the inventiveconcepts.

It will be understood that when an element is referred to as being “on,”“connected” or “coupled” to another element, it can be directly on,connected or coupled to the other element or intervening elements may bepresent. In contrast, when an element is referred to as being “directlyon,” “directly connected” or “directly coupled” to another element,there are no intervening elements present. As used herein the term“and/or” includes any and all combinations of one or more of theassociated listed items. Further, it will be understood that when alayer is referred to as being “under” another layer, it can be directlyunder or one or more intervening layers may also be present. Inaddition, it will also be understood that when a layer is referred to asbeing “between” two layers, it can be the only layer between the twolayers, or one or more intervening layers may also be present.

Example embodiments will be described below with reference toToss-sectional views, which are example drawings of the inventiveconcepts. The example drawings may be modified by manufacturingtechniques and/or tolerances. Accordingly, the example embodiments arenot limited to specific configurations shown in the example drawings,and include modifications based on the example method of manufacturingthe semiconductor device. For example, an etched region shown at arightangle may be formed in a rounded shape or formed to have a given (oralternatively, predetermined) curvature. Therefore, regions shown in thedrawings have schematic characteristics. In addition, the shapes of theregions shown in the example drawings exemplify specific shapes ofregions in an element, and do not limit the inventive concepts. Thoughterms like a first, a second, and a third are used to describe variouselements in various example embodiments of the inventive concepts, theelements are not limited to these terms. These terms are used only totell one element from another element. An example embodiment describedand exemplified herein includes a complementary embodiment thereof.

The terms used in the specification are for the purpose of describingparticular embodiments only and are not intended to be limiting of theinventive concepts. As used in the specification, the singular forms“a”, “an” and “the” are intended to include the plural forms as well,unless the context clearly indicates otherwise. It will be furtherunderstood that the terms “comprises” and/or “comprising”, when used inthe specification, specify the presence of stated features, integers,steps, operations, elements, and/or components, but do not preclude thepresence or addition of one or more other features, integers, steps,operations, elements, components, and/or groups thereof.

It will be understood that, although the terms “first”, “second”, etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer orsection from another element, component, region, layer or section. Thus,a first element, component, region, layer or section discussed belowcould be termed a second element, component, region, layer or sectionwithout departing from the teachings of example embodiments.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the example term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which example embodiments belong. Itwill be further understood that terms, such as those defined incommonly-used dictionaries, should be interpreted as having a meaningthat is consistent with their meaning in the context of the relevant artand will not be interpreted in an idealized or overly formal senseunless expressly so defined herein. As used herein, expressions such as“at least one of,” when preceding a list of elements, modify the entirelist of elements and do not modify the individual elements of the list.

Although corresponding plan views and/or perspective views of somecross-sectional view(s) may not be shown, the cross-sectional view(s) ofdevice structures illustrated herein provide support for a plurality ofdevice structures that extend along two different directions as would beillustrated in a plan view, and/or in three different directions aswould be illustrated in a perspective view. The two different directionsmay or may not be orthogonal to each other. The three differentdirections may include a third direction that may be orthogonal to thetwo different directions. The plurality of device structures may beintegrated in a same electronic device. For example, when a devicestructure (e.g., a memory cell structure or a transistor structure) isillustrated in a cross-sectional view, an electronic device may includea plurality of the device structures (e.g., memory cell structures ortransistor structures), as would be illustrated by a plan view of theelectronic device The plurality of device structures may be arranged inan array and/or in a two-dimensional pattern.

Hereinafter, some example embodiments of the inventive concepts will nowbe described more fully with reference to accompanying example drawings.

FIG. 1, FIGS. 2A and 2B, and FIG. 3 illustrate a block copolymer.

Referring to FIG. 1, a block copolymer is a polymer including two ormore polymer blocks connected to each other through a covalent bond. Forexample, the block copolymer may include a first polymer block and asecond polymer block that may comprise different monomers and havedifferent chemical properties. For example, the first polymer block maybe hydrophilic while the second polymer block may be hydrophobic.

Hereinafter, a block sequence of a first polymer block (A-1)-a secondpolymer block (B-1)-a second polymer block (B-2)-a first polymer block(A-2) will be defined as a single unit. The length of the single unitwill be referred to as unit length L0 of a block copolymer. Within theunit length L0 of the block copolymer, a single first polymer block unit(A-1) and a single second polymer block (B-1) may be covalently bondedto each other, a second polymer block (B-2) having the same chemicalproperties as the second polymer block (B-1) may be bonded to the sideof the second polymer block (B-1), and a first polymer block (A-2) maybe covalently bonded to the side of the second polymer block (B-2).

Referring to FIG. 2A, the block copolymer may be a state in which thefirst and second polymer blocks are mixed disorderly. Referring to FIG.2B, when the block copolymer is annealed, the annealed block copolymermay be self-assembled to first block parts (A) including the firstpolymer block and second block parts including the second polymer block(B).

Referring to FIG. 3, the first and second polymer blocks (A and B) maybe self-assembled to a spherical, cylindrical or lamellar structureaccording to a molar volume ratio between the first and second polymerblocks (A and B). For example, when the first polymer block (A) and thesecond polymer block (B) have a similar molar volume ratio, the firstpolymer block (A) and the second polymer block (B) may be sequentiallystacked to form a lamellar structure that is a layered structure.

When the molar volume ratio of the second polymer block (B) increases,the first polymer block (A) may form a regularly arranged cylindricalstructure and the second polymer block (B) may form a matrix structureto cover the cylindrical structure.

When the molar volume ratio of the second polymer block (B) furtherincreases, the first polymer block (A) may form a regularly arrangedspherical structure and the second polymer block (B) may form a matrixstructure to cover the spherical structure. A reverse phenomenon mayoccur as the molar volume ratio of the first polymer block (A)increases.

Example embodiments of inventive concepts are aimed to fabricate apattern structure having a width greater than a critical dimension (CD)that may be implemented in a photolithography process or a doublepattern technology (DPT) process using properties of a copolymer forminga lamellar structure.

FIGS. 4 to 8 are cross-sectional views illustrating a method offabricate a pattern structure according to some example embodiments ofinventive concepts,

Referring to FIG. 4, mask patterns 110 may be formed on an etch targetlayer 100.

The mask patterns 110 may include a material having an etch selectivitywith respect to the etch target layer 100.

According to an aspect, the etch target layer 100 may include one of asemiconductor material, a conductive material, and an insulatingmaterial or a combination thereof. In some example embodiments, if theetch target layer 100 includes the semiconductor material, the etchtarget layer 100 may be a semiconductor substrate or an epitaxial layer.Alternatively, the etch target layer 100 may include crystallinesilicon, amorphous silicon, doped silicon, silicon germanium or acarbon-based material. In some example embodiments, if the etch targetlayer 100 includes the conductive material, the etch target layer 100may include doped polysilicon, metal silicide, metal, metal nitride or acombination thereof. In some example embodiments, if the etch targetlayer 100 includes the insulating material, the etch target layer 100may include silicon oxide, silicon nitride, silicon oxynitride or alow-k dielectric material.

The mask patterns 110 may include a plurality of openings 112 and 114 toexpose a top surface of the etch target layer 100. In some exampleembodiments, each of the mask patterns 110 may have a line structureextending in one direction and the mask patterns 110 may be parallel toeach other. The mask patterns 110 may have substantially the same widthMWT.

Spaced distances between the mask patterns 110 may be substantiallyequal to each other. Alternatively, the spaced distances between themask patterns 110 may be different from each other. That is, widths ofthe openings 112 and 114 may be substantially equal to each other orsubstantially different from each other. In FIG. 4, the widths of theopenings 112 and 114 are different from each other. In addition, a widthof each of the openings 112 and 114 may be smaller than or substantiallyequal to the unit length L0 of the block copolymer in FIG. 1.Specifically, the openings 112 and 114 may include a first opening 112having a first width WT1 and a second opening 114 having a second widthWT2 smaller than the first width WT1. The first width WT1 may besubstantially equal to the unit length L0 of the block copolymer in FIG.1.

The mask patterns 110 may include one of carbon-based spin on hardmask(C—SOH) and silicon-based SOH (Si—SOH). In this case, the mask patternsmay have a hydrophobic surface.

Referring to FIG. 5, the openings 112 and 114 may be filled with a blockcopolymer material 120 on the etch target layer 110.

The block copolymer material 120 may include at least one selected fromthe group consisting of polystyrene-block-polymethylmethacrylate(PS-b-PMMA), polystyrene-block-polydimethyl siloxane (PS-b-PDMS),polybutadiene-block-polybutylmethacrylate,polybutadiene-block-polydimethylsiloxane,polybutadiene-block-polymethylmethacrylate,polybutadiene-block-polyvinylpyridine,polybutylacrylate-block-polymethylmethacrylate,polybutylacrylate-block-polyvinylpyridine,polyisoprene-block-polyvinylpyridine,polyisoprene-block-polymethylmethacrylate,polyhexylacrylate-block-polyvinylpyridine,polyisobutylene-block-polybutylmethacrylate,polyisobutylene-block-polymethylmethacrylate,polyisobutylene-block-polybutylmethacrylate,polyisobutylene-block-polydimethylsiloxane,polybutylmethacrylate-block-polybutylacrylate,polyethylethylene-block-polymethylmethacrylate,polystyrene-block-polybutylmethacrylate,polystyrene-block-polybutadiene, polystyrene-block-polyisoprene,polystyrene-block-polydimethylsiloxane,polystyrene-block-polyvinylpyridine,polyethylethylene-block-polyvinylpyridine,polyethylene-block-polyvinylpyridine,polyvinylpyridine-block-polymethylmethacrylate,polyethyleneoxide-block-polystyrene,polyethyleneoxide-block-polybutadiene,polyethyleneoxide-block-polystyrene,polyethyleneoxide-block-polymethylmethacrylate,polyethyleneoxide-block-polydimethylsiloxane, polystyrene-block-polyethyleneoxide,polystyrene-block-polymethylmethacrylate-block-polystyrene,polybutadiene-block-polybutylacrylate-block-polybutadiene,polybutadiene-block-polydimethylsiloxane-block-polybutadiene,polybutadiene-block-polymethylmethacrylate-block-polybutadiene,polybutadiene-block-polyvinylpyridine-block-polybutadiene,polybutylacrylate-block-polymethylmethacrylate-block-polybutylacrylate,polybutylacrylate-block-polyvinylpyridine-block-polybutylacrylate,polyisoprene-block-polyvinylpyridine-block-polyisoprene,polyisoprene-block-polymethylmethacrylate-block-polyisoprene,polyhexylacrylate-block-polyvinylpyridine-block-polyhexylacrylate,polyisobutylene-block-polybutylmethacrylate-block-polyisobutylene,polyisobutylene-block-polymethylmethacrylate-block-polyisobutylene,polyisobutylene-block-polybutylmethacrylate-block-polyisobutylene,polyisobutylene-block-polydimethylsiloxane-block-polyisobutylene,polybutylmethacrylate-block-polybutylacrylate-block-polybutylmethacrylate,polyethylethylene-block-polymethylmethacrylate-block-polyethylethylene,polystyrene-block-polybutylmethacrylate-block-polystyrene,polystyrene-block-polybutadiene-block-polystyrene,polystyrene-block-polyisoprene-block-polystyrene,polystyrene-block-polydimethylsiloxane-block-polystyrene,polystyrene-block-polyvinylpyridine-block-polystyrene,polyethylethylene-block-polyvinylpyridine-block-polyethylethylene,polyethylene-block-polyvinylpyridine-block-polyethylene,polyvinylpyridine-block-polymethylmethacrylate-block-polyvinylpyridine,polyethyleneoxide-block-polystyrene-block-polyethyleneoxide,polyethyleneoxide-block-polybutadiene-block-polyethyleneoxide,polyethyleneoxide-block-polystyrene-block-polyethyleneoxide,polyethyleneoxide-block-polymethacrylate-block-polyethyleneoxide,polyethyleneoxide-block-polydimethylsiloxane-block-polyethyleneoxide,and polystyrene-block-polyethyleneoxide-block-polystyrene. According tosome example embodiments of inventive concepts, the block copolymermaterial 120 is not limited to the above-mentioned materials.

After one of the above-mentioned materials is selected, i.e., a selectedblock copolymer material 120 is dissolved in solvent, a block polymerlayer is formed by means of spin coating, etc. The solvent may be almostvaporized after the spin coating.

According to example embodiments, the block copolymer material 120 maybe PS-b-PMMA. In this case, a molar volume ratio between polystyrene(PS) and poly-methyl-meta-acrylate (PMMA) may be 4:6 or 6:4. The unitlength L0 of a block copolymer of the PS-b-PMMA (see FIG. 1) may beabout 30 nm.

Retelling to FIG. 6, the block copolymer material 120 may beself-assembled to first block patterns 120 a including first polymerblocks and second patterns 120 b including second polymer blocks byannealing the block copolymer material 120. The annealing may includeone of solvent annealing, ultraviolet annealing, and thermal annealing.

When the block copolymer material 120 is PS-b-PMMA, each of the firstpatterns 120 may include PS (hydrophobic) and each of the secondpatterns 120 b may include PMMA (hydrophilic). Thus, the first patterns120 a may be disposed at a side surface of the hydrophobic mask patterns110. A second pattern 120 b may be disposed closely adjacent to therespective first patterns 120 a.

As set forth above, the openings 112 and 114 may include the firstopening 112 having substantially the same width as the unit length L0 ofthe block copolymer and the second opening 114 having a second width WT2smaller than the first width WT1. As shown in FIG. 6, first pattern 120a-second pattern 120 b-second pattern 120 b-first pattern 120 a may bearranged horizontally in the first opening 112. The total horizontallength of the first pattern 120 a-the second pattern 120 b-the secondpattern 120 b-the first pattern 120 a may be substantially equal to theunit length L0 of the block copolymer (see FIG. 1). The first polymerblocks may be vertically opposite to each other in the respective firstpatterns 120 a, and the second polymer blocks may be vertically oppositeto each other in the respective second patterns 120 b.

The first pattern 120 a-the second pattern 120 b-the second pattern 120b-the first pattern 120 a may also be arranged horizontally in the firstopening 112. Although the first pattern 120 a-the second pattern 120b-the second pattern 120 b-the first pattern 120 a arranged in the firstopening 112 are a single unit of a block copolymer, their totalhorizontal length may be smaller than the unit length L0 of the blockcopolymer. In this case, PS of the first pattern 120 a may be shrunk asa polymer and a block copolymer corresponding to the unit length L0 ofthe block copolymer may be arranged even within a width smaller than theunit length L0 of the block copolymer.

As shown in FIG. 6, the second patterns 120 b disposed in the first andsecond openings 112 and 114 having different widths WT1 and WT2 may havesubstantially the same width AWT. Spaced distances between the secondpatterns 120 b may also be substantially equal to each other.

When the surfaces of the mask patterns 110 are modified to behydrophilic, the first patterns 120 a cannot be arranged on sidewalls ofthe mask patterns 110. Thus, the surfaces of the mask patterns 110 maybe made hydrophobic.

In some example embodiments, a material having a —OH group such as PS—OHand 2-hydroxyethyl methacrylate (HEMA) may be provided to the surfacesof the mask patterns 110 to form a PS-brush layer (not shown) on ahydrophilic surface through CO₂H or Si—OH bond. The first patterns 120 aincluding PS may be arranged on the hydrophilic surfaces of the maskpatterns 110 by the PS-brush layer.

The PS—OH is represented by Formula (1), and the HEMA is represented byFormula (2).

Referring to FIG. 7, the second patterns 120 b may be selectivelyremoved to form etch patterns 130 including the mask patterns 110 andthe first patterns 120 a. Third openings 135 defined by the etchpatterns 130 may be formed by means of a process of removing the secondpatterns 120 b.

According to an aspect, the sum of widths of a single etch pattern 130and a single third opening 135 is called a pitch PTC. Pitches PTC may besubstantially equal to each other.

In some example embodiments, when the first pattern 120 a includes PSand the second patterns 120 b includes PMMA, the second patterns 120 bmay be removed by means of a dry etch process using oxygen (O₂). Insonic example embodiments, after irradiating deep ultraviolet (UV) tothe second pattern 120 b, the second patterns 120 b may be developedwith isopropyl alcohol (IPA) or an acetone-based material to be removed.

Referring to FIG. 8, the etch target layer 100 may be etched using theetch patterns 130 as etch masks to fabricate a desired patternstructure.

The pattern structure may include a plurality of patterns PT, widths PWTof the patterns PT may be substantially equal to each other, and spaceddistances between the patterns PT may be substantially equal to eachother.

FIGS. 9 to 13 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

Referring to FIG. 9, openings 112 and 114 defined by mask patterns 110formed on an etch target layer 100 may be filled with a block copolymermaterial 120. The step of forming the mask patterns 110 on the etchtarget layer 100 is substantially identical to that described withreference to FIG. 4 and will not be described in further detail.

In the example embodiments, the block copolymer material 120 may bepolystyrene-block-polydimethylsiloxane (PS-b-PDMS). In this case, amolar volume ratio between polystyrene (PS) and polydimethylsiloxane(PDMS) may be 4:6 or 6:4. The unit length L0 of the block copolymer ofthe PS-b-PDMS (see FIG. 1) may be about 30 nm.

Referring to FIG. 10, a neutral layer 125 may be formed on the maskpatterns 110 filled with the block copolymer material 120.

Due to properties of the PS-b-PDMS, during a subsequent annealingprocess, it may be difficult to achieve vertically opposite arrangementof first polymer blocks in the respective first patterns 120 a (see FIG.11) and to achieve vertically opposite arrangement of second polymerhocks in the respective second patterns 120 b (see FIG. 11).Accordingly, it may be easy to achieve vertically opposite arrangementof the first polymer blocks in the respective first patterns 120 a andto achieve vertically opposite arrangement of the second polymer blocksin the respective second patterns 12 b.

The neutral layer 125 may include one of a self-assembled monolayer(SAM), a polymer brush, and a cross-linked random copolymer mat.

The self-assembled monolayer (SAM) may include at least one selectedfrom the group consisting of phenethyltrichlorosilane (PETCS),phenyltrichlorosilane (PTCS), benzyltrichlorosilane (BZTCS),tolyltrichlorosilane (TTCS), 2-[(trimethoxysilyl)ethyl]-2-pyridine(PYRTMS), 4-biphenylyltrimethoxysilane (BPTMS), octadecyltrichlorosilane(OTS), 1-naphthyltrimethoxysilane (NAPTMS),1-[(trimethoxysilyl)methyl]naphthalene (MNATMS), and(9-methylanthracenyl)trimethoxysilane (MANTMS).

The polymer brush may have a form in which a hydrophilic polymer and ahydrophobic polymer are randomly bonded to each other. The polymer brushmay be called a brush-type random copolymer. The polymer brush may be,for example, polystyrenerandom-poly(methymethacrylate) (PS-r-PMMA).

The cross-linked random copolymer mat may be abenzocyclobutene-functionalized polystyrene-r-poly(methacrylate)copolymer including benzocyclobutene.

Referring to FIG. 11, the block copolymer material 120 may beself-assembled to the first patterns 120 a and the second patterns 120 bby annealing the block copolymer material 120. The annealing may includeone of solvent annealing, ultraviolet annealing, and thermal annealing.

When the block copolymer material 120 is PS-b-PMMA, each of the firstpatterns 120 may include PS (hydrophobic) and each of the secondpatterns 120 b may include PMMA (hydrophilic). Thus, the first patterns120 a may be disposed at a side surface of the hydrophobic mask patterns110. A second pattern 120 b may be disposed closely adjacent to therespective first patterns 120 a.

The openings 112 and 114 may include the first opening 112 havingsubstantially the same width as the unit length L0 of the blockcopolymer and the second opening 114 having a second width WT2 smallerthan the first width WT1. As shown in FIG. 11, the total horizontallength of the first pattern 120 a-the second pattern 120 b-the secondpattern 120 b-the first pattern 120 a may be substantially equal to theunit length L0 of the block copolymer (see FIG. 1). The first polymerblocks may be vertically opposite to each other in the respective firstpatterns 120 a, and the second polymer blocks may be vertically oppositeto each other in the respective second patterns 120 b.

The first pattern 120 a-the second pattern 120 b-the second pattern 120b-the first pattern 120 a may also be arranged horizontally in the firstopening 112. Although the first pattern 120 a-the second pattern 120b-the second pattern 120 b-the first pattern 120 a arranged in the firstopening 112 are a single unit of a block copolymer, their totalhorizontal length may be smaller than the unit length L0 of the blockcopolymer. In this case, PS of the first pattern 120 a may be shrunk asa polymer and a block copolymer corresponding to the unit length L0 ofthe block copolymer may be arranged even within a width smaller than theunit length L0 of the block copolymer.

As shown in FIG. 11, the second patterns 120 b disposed in the first andsecond openings 112 and 114 having different widths WT1 and WT2 may havesubstantially the same width AWT.

When the surfaces of the mask patterns 110 are modified to behydrophilic, a PS-brush layer (not shown) may be formed on the surfacesof the mask patterns 110. The step of forming the PS-brush layer hasbeen described above and will not be described in further detail.

Referring to FIG. 12, the second patterns 120 b may be allowed to remainby selectively removing the first patterns 120 a and the mask patterns110.

Spaced distances SP between the second patterns 120 b may besubstantially equal to each other. In the example embodiments, thesecond patterns 120 b may include PDMS.

In case of PS-b-PMMA, an etch selectivity of PMMA (second pattern 120 b)is higher than that of PS (first pattern 120 a) and both the PS and thePMMA are organic polymers. Accordingly, it may be difficult toselectively remove only the PMMA.

However, since the PDMS includes silicon (Si), the silicon of the PDMSmay be bonded to oxygen (O₂) to modify PDMS of the second patterns 120 binto SiO₂ while the PS and the mask patterns 110 are removed by means ofa dry etch process using the oxygen (O₂).

Referring to FIG. 13, the etch target layer 100 may be etched using thesecond patterns 120 b as etch masks to fabricate a desired patternstructure.

The pattern structure may include a plurality of patterns PT, widths PWTof the patterns PT may be substantially equal to each other, and spaceddistances between the patterns PT may be substantially equal to eachother. In addition, width PWT of each pattern of the pattern structuremay be smaller than the width MWT of each of the mask patterns 110 (seeFIG. 9).

FIGS. 14 to 17 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

Referring to FIG. 14, mask patterns 110 may be formed on an etch targetlayer 100. The mask patterns 110 may include a plurality of openings115, 116, and 117 to expose a top surface of the etch target layer 100.

In the example embodiments, widths MWT of the mask patterns 110 may beequal to each other but spaced distances WT1, WT2, and WT3 between themask patterns 110 may be different from each other. That is, theopenings 115, 116, and 117 may include a first opening 115 having widthWT1 smaller than unit length L0 of a block copolymer, a second opening116 having width WT2 greater than the unit length L0 of the blockcopolymer, and a third opening 117 having substantially the same widthWT3 as the unit length L0 of the block copolymer. The second opening 116may have a width that is double the unit length L0 of the blockcopolymer.

Referring to FIG. 15, after filling the openings 115, 116, and 117 witha block copolymer material 120, they may be annealed to form firstpatterns 120 a and second patterns 120 b in the respective openings 115,116, and 117.

In some example embodiments, the block copolymer material 120 may bePS-b-PMMA. In this case, the first patterns 120 a may include PS and thesecond patterns 120 b may include PMMA.

In some example embodiments, the block copolymer material 120 may bePS-b-PDMS. In this case, the first patterns 120 a may include PS and thesecond patterns 120 b may include PDMS. Prior to the annealing, aneutral layer 125 see FIG. 10) may be further formed.

As mentioned above, in each of the first and third openings 115 and 117,first pattern 120 a-second pattern 120 b-second pattern 120 b-firstpattern 120 a corresponding to the unit length L0 of the block copolymermay be vertically opposite to be arranged horizontally. In the secondopening 114, first pattern 120 a-second pattern 120 b-second pattern 120b-first pattern 120 a corresponding to double the unit length L0 of theblock copolymer may be vertically opposite to be arranged horizontally.As described in FIG. 15, the second opening 114 has a width that isdouble the length L0 of the block copolymer. However, some exampleembodiments of inventive concepts are not limited to the description.

Referring to FIG. 16, when the block copolymer material 120 isPS-b-PMMA, only the second patterns 120 may be selectively removed andthen the etch target layer 100 may be etched using etch patterns 130including the first patterns 120 a and the mask patterns 110 as etchmasks to fabricate a pattern structure PT.

Referring to FIG. 17, when the block copolymer material 120 isPS-b-PDMS, the first patterns 120 a and the mask patterns 110 may beremoved and then the etch target layer 110 may be etched using thesecond patterns 120 b as etch masks to fabricate a pattern structure PT.

The omitted explanations of the example embodiments may refer to theexplanations in FIGS. 1 to 13.

FIGS. 18 to 22 are cross-sectional views illustrating a method offabricating a pattern structure according to some example embodiments ofinventive concepts.

Referring to FIG. 18, a mask layer 155 and sacrificial patterns 160 maybe sequentially formed on an etch target layer 150.

The etch target layer 150, the mask layer 155, and the sacrificialpatterns 160 may include different materials. The etch target layer 150may include a material having an etch selectivity with respect to themask layer 155, the mask layer 155 may include an etch selectivity withrespect to the etch target layer 150 and the sacrificial patterns 160,and the sacrificial patterns 160 may include a material having an etchselectivity with respect to the mask layer 155.

The etch target layer 150 may include one of a semiconductor material, aconductive material, and an insulating material or a combinationthereof. In some example embodiments, if the etch target layer 150includes the semiconductor material, the etch target layer 150 may be asemiconductor substrate or an epitaxial layer. Alternatively, the etchtarget layer 150 may include crystalline silicon, amorphous silicon,doped silicon, silicon germanium or a carbon-based material. In someexample embodiments, if the etch target layer 100 includes theconductive material, the etch target layer 150 may include dopedpolysilicon, metal silicide, metal, metal nitride or a combinationthereof. In some example embodiments, if the etch target layer 150includes the insulating material, the etch target layer 150 may includesilicon oxide, silicon nitride, silicon oxynitride or a low-k dielectricmaterial.

The mask layer 155 may include one of carbon-containing SOH (C—SOH) andsilicon-containing SOH (Si—SOH).

Each of the sacrificial patterns 160 may include one of a photoresistmaterial and an SOH material. Alternatively, the sacrificial patterns160 may include one selected from the group consisting ofsilicon-containing materials such as polysilicon, SiON, Si₃N₄, and SiCN.Each of the sacrificial patterns 160 may be a linear structure extendingin one direction, and the sacrificial patterns 160 may be parallel toeach other.

Referring to FIG. 19, spacers 165 having the same width WT1 may beformed on both sidewalls of each of the sacrificial patterns 160.

More specifically, a spacer layer (not shown) may be conformally formedon the mask layer 155 and the sacrificial patterns 160. The spacer layermay include a material having an etch selectivity with respect to themask layer 155 and the sacrificial patterns 160. For example, the spacerlayer may include at least one of silicon oxide, silicon nitride, andsilicon oxynitride.

The spacer layer may be anisotropically etched to form spacers 165having a first width WT1 on both sidewalls of each of the sacrificialpatterns 160. The spacers 165 may also extend in the same direction asthe sacrificial pattern 160.

In the example embodiments, the sacrificial patterns 160 and the spacers165 must be formed to have the same width WT1. However, as a criticaldimension (CD) of the sacrificial patterns 160 decreases, a width of thesacrificial pattern 160 is made smaller than the first width WT1 of thespacers 165 to decrease a distance between a single spacer 165 and anadjacent single sacrificial pattern 160, which is called “pitch waking”.

Hereinafter, the critical dimension of the spacer 165 will be referredto as a first width WT1 and the critical dimension of the sacrificialpattern 160 will be referred to as a second width WT2. The second widthWT2 may be smaller than the first width WT1. Width of a portion wherethe sacrificial pattern 160 is not formed, i.e., width of a spacebetween spacers 165 facing each other may be substantially equal to thefirst width WT1. Hereinafter, the space will be referred to as a firstopening 170. When the pitch walking does not occur, the spacers 165 maybe spaced apart from each other by the first width WT1 by thesacrificial pattern 160 or the space.

Referring to FIG. 20, the sacrificial patterns 160 may be selectivelyremoved such that second openings 172 are formed to expose a top surfaceof the mask layer 155 by the second width WT2.

The first opening 170 may have the first width WT1, and the secondopening 172 may have the second width WT2 smaller than the first widthWT1. Thus, spaced distances between the spacers 165 may be differentfrom each other.

Retelling to FIG. 21, the mask layer 155 may be etched using patterns ofthe spacer 165 as etch masks to form mask patterns 175.

The mask patterns 175 may have a structure corresponding to the patternsof the spacer 165. That is, each of the mask patterns 175 may extend inthe one direction and the mask patterns 175 may be parallel to eachother. Each of the mask patterns 175 may have the first width WT1. Eachof the first and second openings 172 and 172 may extend to a spacebetween the mask patterns 175.

The mask patterns 175 may include an SOFT material to intrinsically havea hydrophobic property. However, the mask patterns 175 may have ahydrophilic property because an etch process of the mask layer 155 isconventionally performed as a dry etch process using oxygen and theoxygen may bonded to carbon or silicon of the mask patter 175.

Referring to FIG. 22, after the patterns of the spacer 165 are removed,the first and second openings 112 and 114 between the mask patterns 175may be filled with the block copolymer material 180.

In a subsequent process, a desired pattern structure may be fabricatedby means of the process described with reference to FIGS. 4 to 8 or theprocess described with reference to FIGS. 9 to 13.

FIGS. 23 and 24 are cross-sectional views illustrating a semiconductordevice according to some example embodiments of inventive concepts.

Referring to FIGS. 23 and 24, the semiconductor device may include asubstrate 200/301 and a pattern structure disposed on the substrate200/301.

The substrate 200/301 may include a cell region in which memory cellsare disposed and a peripheral circuit region formed adjacent to the cellregion. The peripheral region may include logic patterns for the memorycells or input/output (I/O) patterns to input/output an electricalsignal to the memory cells. In the example embodiments, the patternstructure may be fabricated in the peripheral region.

The pattern structure may include patterns 210/311 of a linear structureextending in one direction. The patterns 210/311 may be parallel to eachother, and the patterns 210/311 may have substantially the same widthWT. In some example embodiments, spaced distances SP between thepatterns 210/311 may be substantially equal to each other. In someexample embodiments, the spaced distances SP between the patterns210/311 may be different from each other. Each of the patterns 210/311may be formed by means of the process described with reference to FIGS.4 to 8 or the process described with reference to FIGS. 9 to 13.

In some example embodiments, the pattern structure may include aplurality of metal interconnections 210 that extend in one direction andare parallel to each other, as shown in FIG. 23.

In some example embodiments, the pattern structure may include a deviceisolation layer 305 to define fin active patterns 311 and a gatestructure 307 intersecting the device isolation layer 305. A top surfaceof each of the fin active patterns 311 may be higher than that of thedevice isolation layer 305. In the example embodiments, the patterns maycorrespond to the fin active patterns 311.

FIG. 25 is a block diagram illustrating an example of an electronicsystem including a semiconductor device fabricated according to someexample embodiments of inventive concepts.

Referring to FIG. 25, an electronic system 1100 may include a controller1110, an input/output (I/O) device 1120, a memory device 1130, aninterface 1140, and a bus 1150. The controller 1100, the I/O device1120, the memory device 1130, and/or the interface 1140 may be connectedto each other via the bus 1150. The bus 1150 corresponds to a path alongwhich data are transmitted.

The controller 1110 may include at least one of a microprocessor, adigital signal processor, a microcontroller, and logic elements capableof performing similar functions to those of a microprocessor, a digitalsignal processor and a microcontroller. The I/O device 1120 may includea keypad, a keyboard, and a display device. The memory device 1130 maystore data and/or commands. When semiconductor devices according to theforegoing example embodiments of the inventive concepts are implementedusing semiconductor memory device, the memory device 1130 may include atleast one of semiconductor memory device described in the foregoingexample embodiments. The interface 1140 may be used to transmit/receivedata to/from a communication network. The interface 1140 may be a wiredor wireless interface. In some example embodiments, the interface 1140may include an antenna or a wired/wireless transceiver. Although notshown, the electronic system 1100 may include an operating memory forimproving the operation of the controller 1110 and may further include ahigh-speed dynamic random access memory (DRAM) and/or SRAM.

The electronic system 1100 may be applied to all types of electronicproducts capable of transmitting and/or receiving information in awireless environment, such as a personal digital assistant (PDA), aportable computer, a web tablet, a wireless phone, a mobile phone, adigital music player, and a memory card.

FIG. 26 is a block diagram of a memory card 1200 including asemiconductor device fabricated according to some example embodiments ofthe inventive concepts.

Referring to FIG. 26, a memory card 1200 for supporting high-capacitydata storage capability includes a memory device 1210 including asemiconductor device according to some example embodiments of theinventive concepts. The memory card 1200 includes a memory controller1220 to control data exchange between a host and the memory device 1210,

An SRAM 1221 is used as a working memory of the processing unit 1222. Ahost interface 1223 may include a data exchange protocol of a hostconnected with the memory card 1200. An error correct on code block(ECC) 1224 detects and corrects an error of data read from the memorydevice 1210. A memory interface 1225 interfaces with the flash memorydevice 1210. The processing unit 1222 performs an overall controloperation for data exchange of the memory controller 1220. Although notillustrated in figures, it will be understood by those skilled in theart that the memory card 1200 may further include a ROM to store codedata for interfacing with the host.

As described so far, a pattern structure including patterns having acritical dimension (CD) may be fabricated between mask patterns using ablock copolymer material although it is difficult to achieve the CDusing an extreme ultraviolet (EUV) or double patterning technology (DPT)process. Moreover, widths of patterns formed using properties of a blockcopolymer material may be substantially equal to each other. Thus,process reliability may be improved.

While the example inventive concepts have been particularly shown anddescribed with reference to example embodiments thereof, it will beapparent to those of ordinary skill in the art that various changes inform and detail may be made therein without departing from the spiritand scope of the inventive concepts, which is defined by the followingclaims.

What is claimed is:
 1. A method comprising: forming mask patterns on anetch target layer, the mask patterns spaced apart from each other by atleast one opening; filling the opening with a block copolymer materialincluding first and second polymer blocks of different properties; andannealing the block copolymer material to form first patterns and secondpatterns, the first patterns in contact with facing sidewalls ofadjacent ones of the mask patterns, respectively, and at least one ofthe second patterns between the first patterns,the first patternsincluding the first polymer blocks and the second patterns including thesecond polymer blocks.
 2. The method as set forth in claim 1, whereinthe forming forms the mask patterns such that the opening has a widthsmaller than or equal to a length of a unit of a block sequence in theblock copolymer material, the block sequence including the first polymerblock-the second polymer block-the second polymer block-the firstpolymer block.
 3. The method as set forth in claim 2, wherein the firstpolymer block-the second polymer block-the second polymer block-thefirst polymer block of the block sequence are arranged sequentially fromone of the facing sidewalls of the adjacent mask patterns to another ofthe facing sidewalls of the adjacent mask patterns in a horizontaldirection.
 4. The method as set forth in claim 2, wherein: each of themask patterns is hydrophobic; each of the first patterns is hydrophobic;and the second pattern is hydrophilic.
 5. The method as set forth inclaim 2, wherein: the block copolymer material includespolystyrene-block-polymethylmethacrylate (PS-b-PMMA); the first polymerblock includes polystyrene (PS); and the second polymer block includespolymethylmethacrylate (PMMA).
 6. The method as set forth in claim 5,further comprising: selectively removing the second patterns; andetching the etch target layer using the first patterns and the maskpatterns as etch masks to form the pattern structure.
 7. The method asset forth in claim 1, wherein: the block copolymer material includespolystyrene-block-polydimethylsiloxane (PS-b-PDMS); the second polymerblock includes polystyrene (PS); and the second polymer block includespolydimethylsiloxane (PDMS)
 8. The method as set forth in claim 7,further comprising: forming a neutral layer on the block copolymermaterial and the mask patterns before the annealing.
 9. The method asset forth in claim 7, further comprising: removing the first patternsand the mask patterns; and etching the etch target layer using thesecond patterns as an etch mask to form the pattern structure.
 10. Themethod as set forth in claim 1, wherein: the forming forms the maskpatterns extending in one direction, and having widths equal to eachother; and the opening includes a first opening having a first width anda second opening having a second width smaller than the first width. 11.The method as set forth in claim 10, wherein the forming forms the maskpatterns such that the opening has a first width equal to a length of aunit of a block sequence in the block copolymer material, the blocksequence including the first polymer block-the second polymer block-thesecond polymer block-the first polymer block.
 12. The method as setforth in claim 1, wherein the forming forms surfaces of the maskpatterns to be hydrophilic, further comprising: hydrophobicallymodifying the hydrophilic surfaces of the mask patterns.
 13. The methodas set forth in claim 12, wherein: each of the first patterns ishydrophobic; and the second pattern is hydrophilic.
 14. A methodcomprising: forming a mask layer on an etch target layer; forming asacrificial pattern on the mask layer extending in a first direction,the sacrificial pattern having a linear structure of a first width;forming spacers on sidewalls of the sacrificial pattern to define afirst opening exposing a top surface of the mask layer, the firstopening having a second width different from the first width; removingthe sacrificial pattern to form a second opening having the first width;etching the mask layer using the spacers as etch masks to form maskpatterns, the mask patterns defining a third opening having the firstwidth and a fourth opening having the second width; filling each of thethird and fourth openings with a block copolymer material includingfirst and second poly r blocks of different properties, and annealingthe block copolymer material to form first patterns and second patterns,the first patterns in contact with facing sidewalls of adjacent ones ofthe mask patter s, respectively, and at least one of the second patternsbetween the first patterns, the first patterns including the firstpolymer blocks and the second patterns including the second polymerblocks.
 15. A method comprising: forming a block copolymer layer betweenadjacent mask patterns, the block copolymer layer including firstpolymer blocks and second polymer blocks different from the firstpolymer blocks; and annealing the block copolymer layer in order to formfirst polymer block patterns and at least one second polymer blockpattern, the first polymer block patterns at respective sidewalls of theadjacent mask patterns and the at least one second polymer block patternbetween the first polymer block patterns, the first polymer blockpatterns including the first polymer blocks and the at least one secondpolymer block pattern including the second polymer blocks.
 16. Themethod as set forth in claim 15, wherein the block copolymer layer isformed in a trench between the adjacent mask patterns, the trench has awidth that is smaller than or equal to a length of a unit of a blocksequence of the block copolymer layers, and the block sequence includesthe first polymer block-the second polymer block-the second polymerblock-the first polymer block.
 17. The method as set forth in claim 16,wherein the first polymer block-the second polymer block-the secondpolymer block-the first polymer block of the block sequence are arrangedsequentially from one of the sidewalls of the adjacent mask patterns toanother of the sidewalls of the adjacent mask patterns in a horizontaldirection.
 18. The method as set forth in claim 15, further comprising:forming the mask patterns on an etch target layer; selectively removingthe at least one second polymer block pattern after the annealing; andetching the etch target layer using the first polymer block patterns andthe mask patterns as etch masks to form the pattern structure.
 19. Themethod as set forth in claim 15, further comprising: forming the maskpatterns on an etch target layer; removing the first polymer blockpatterns and the mask patterns after the annealing; and etching the etchtarget layer using the at least one second polymer block pattern as anetch mask to form the pattern structure.
 20. The method as set forth inclaim 15, further comprising: forming a neutral layer on the blockcopolymer layer and the mask patterns before the annealing.